CN110252272A - A kind of method and device of continuous large scale preparation olefin epoxidation catalysts - Google Patents
A kind of method and device of continuous large scale preparation olefin epoxidation catalysts Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C07D301/00—Preparation of oxiranes
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
The present invention relates to a kind of methods of continuous large-scale production olefin epoxidation catalysts, this method is prepared using the rotary furnace reactor successive reaction of four sequential connections, preparation step includes: that four rotary furnaces are risen to reaction temperature by (1) respectively, and are continuously passed through reactant vapor and/or carrier gas respectively；(2) carrier granular is continuously added to rotary furnace, and continuous successively progress activated centre vapor deposition, high-temperature process, water process and silanization treatment；(3) outlet material is collected in cooling.Invention also provides the continuous large-scale production devices for realizing above-mentioned preparation method.Method and device provided by the invention, realizes the large-scale continuous production of epoxidation catalyst, and the catalyst of acquisition can be used for the industrialized productions such as epoxidation of propylene, activity with higher and yield.
Description
Technical field
The invention belongs to field of catalyst preparation, and in particular to a kind of continuous large scale preparation olefin epoxidation catalysts
Method and device.
Background technique
With ethylbenzene hydroperoxide (EBHP) for the ethylbenzene cooxidation technique (PO/SM) of oxidant and with isopropyl benzene hydroperoxide
It (CHP) is to produce two kinds of important process of propylene oxide (PO) for the CHP technique of oxidant, both techniques overcome chlorohydrination
Corrosion is big, the disadvantages of sewage is more, have many advantages, such as that product cost is low and environmental pollution is small.Both technique used catalysts are
Large aperture Ti-Si molecular sieve or Ti-SiO2Composite oxides, it was reported that catalyst service life≤1 year, but a set of annual output 30
For the commercial plant catalyst annual requirement of ten thousand tons of PO just at 200 tons or more, catalyst amount is very big.
Patent CN1250775A, CN1248579A is disclosed using ethylbenzene hydroperoxide as oxidant, Ti-MCM-41 molecular sieve
The technique that epoxidation of propylene produces propylene oxide is carried out for catalyst；United States Patent (USP) US5783167 discloses hydro-thermal method synthesis and contains
The method of titanium mesoporous material Ti-MCM-41 is disclosed using isopropyl benzene hydroperoxide as oxidant in patent US6323147, Ti-
MCM-41 molecular sieve is the technique of catalyst preparation propylene oxide；SUMITOMO CHEMICAL company (Sumitomo) also discloses that one kind has
The synthetic method of the titanium-containing catalyst Ti-MCM-41 of meso-hole structure；Patent CN106582809A discloses a kind of modifying titanium-silicon point
The synthetic method of son sieve, molecular sieve bore diameter are 10nm or more.The above method is all made of hydro-thermal method synthetic catalyst, by using spy
The template for determining molecular weight and structure carries out catalyst preparation, water heating kettle synthesis point using reaction kettle under high temperature hydrothermal condition
It needs to obtain molecular screen primary powder through drying, demoulding and calcination process after son sieve, then epoxidation catalyst is prepared through molding, it is such
Large pore molecular sieve synthesis technology is complicated, needs to lead to catalyst preparation high expensive, together using a large amount of template in synthesis process
When complex forming technology, limit its large-scale production and application in the industry.
In patent US3829392, US3923843, US4021454, one kind is disclosed with macro-pore SiO2For carrier, pass through gas
Phase sedimentation or liquid-phase impregnation process load to titanium source on carrier surface, through drying, roasting and silanization treatment and etc. obtain
Ti-Si catalyst.But vapour deposition process has the following disadvantages: carrying out intermittently operated, preparation process using fixed bed reactors
It is cumbersome, it is complicated for operation, frequent switching need to be carried out between each step, technological parameter is more and not easy to control；Simultaneously because macropore
SiO2Density is small, and thermal coefficient is low, causes catalyst preparation time long, limits its large-scale production.
In conclusion current conventional epoxidation catalyst preparation method exists, preparation process is complicated for operation, prepares effect
Rate is relatively low, is difficult to realize the problem of industrializing continuous large-scale production.
Summary of the invention
In view of the above-mentioned problems, the present invention provide a kind of easy to operate, preparation efficiency it is high industrialize it is continuous extensive raw
The method for producing epoxidation catalyst.
The present invention also provides a kind of device for realizing above-mentioned method for preparing catalyst simultaneously.
To achieve the above object of the invention, technical scheme is as follows:
A kind of method of continuous large scale preparation olefin epoxidation catalysts, this method use the revolution of four sequential connections
Furnace reactor successive reaction prepares catalyst, and preparation step is as follows:
(1) four rotary furnaces of 1#, 2#, 3# and 4# are followed successively by by sequence by raw material, rise to respective reaction temperature respectively
Degree, and it is continuously passed through respective reactant vapor and/or carrier gas respectively, stablize each in-furnace temperature and gas composition；
(2) carrier granular is continuously added to 1# rotary furnace, and continuously passes sequentially through 1#, 2#, 3# and 4# rotary furnace, in each furnace
It is middle to carry out activated centre vapor deposition, four high-temperature process, water process and silanization treatment reaction steps respectively；
(3) 4# rotary furnace outlet material is collected in cooling, and olefin epoxidation catalysts finished product is prepared.
The advantages of being carried out continuously catalyst preparation using the rotary furnace of four different temperatures is: carrier S iO2Thermal coefficient
It is very low, about 7.6W/mK, if low using other heating method heating efficiencies；Meanwhile each step temperature of catalyst preparation
It is larger to spend difference, intermittently operated needs frequent heating and cooling, and complicated for operation, efficiency is relatively low；And the rotary furnace of four different temperatures is used,
It is just not necessarily to switch reactant vapor the serialization, it can be achieved that catalyst preparation, greatly improves the preparation efficiency of catalyst.
In step (1) of the present invention, the reaction temperature of the 1# rotary furnace is 150~300 DEG C, and the gas being passed through is titanizing conjunction
Object steam and N2Carrier gas；The concentration of titanium compound steam is 5~15%v/v；Titanium compound be selected from titanium tetrafluoride, titanium tetrachloride,
One of titanium tetrabromide, tetraethyl titanate, metatitanic acid orthocarbonate and butyl titanate are a variety of；
In step (1) of the present invention, the reaction temperature of the 2# rotary furnace is 500~800 DEG C, the gas being passed through be purity >=
99.5% N2；
In step (1) of the present invention, the reaction temperature of the 3# rotary furnace is 250~400 DEG C, and the gas being passed through is water vapour
And N2Carrier gas, wherein water vapour is that deionized water is obtained through evaporation gasification, not metal ion；Water vapor concentration in mixed gas
For 5~10%v/v；
In step (1) of the present invention, the reaction temperature of the 4# rotary furnace is 150~300 DEG C, and the gas being passed through is organosilicon
Alkane steam and N2Carrier gas, wherein organosilan be selected from hexamethyldisilazane, hexamethyl chlorine silazane, seven methyl chloride silazane,
Trim,ethylchlorosilane, dimethylchlorosilane, tetramethyl-disilazane, dimethyl diethoxysilane, trimethylmethoxysilane,
One of dimethyldimethoxysil,ne and trimethylethoxysilane are a variety of, preferably hexamethyldisilazane；Gaseous mixture
The concentration of organosilan steam is 10~25%v/v in body.
It will be preheated in step (1) of the present invention and each lead into each revolution with each consistent mixed gas of rotary furnace reaction temperature
Furnace, gas flow are 5~20m3/h；Rotary furnace revolving speed is 3~10r/min.The process conditions help to realize in each rotary furnace
Temperature is uniformly distributed, and guarantees the continuity of catalyst preparation process.
Carrier described in step (2) of the present invention is the SiO after being dried2Material, preferably silica gel particle；Its size distribution
For 0.2~2mm, aperture is 5~15nm, and specific surface area is 200~500m2/ g, water content≤2wt%.
Step (2) carrier of the present invention is added from 1# rotary furnace entrance, and charging rate is constant, and speed is 100~400kg/h；
Reaction time of the carrier in each rotary furnace is 2~6h.
By being connected with the transmission device delivery vehicles particle of nitrogen atmosphere between each rotary furnace of step (2) of the present invention.
Step (2) of the present invention during the reaction, needs the respective preheating reactant vapor of continuous supplementation 1#-4# rotary furnace
And/or carrier gas, stablize each in-furnace temperature and gas composition.
It is screened to obtain finished catalyst after step (3) 4# rotary furnace outlet material of the present invention is cooled to room temperature.
A kind of device preparing the catalyst, which includes the rotary furnace reactor of four sequential connections, by raw material
By being sequentially followed successively by 1# rotary furnace, 2# rotary furnace, 3# rotary furnace and 4# rotary furnace；Pass through spiral between four rotary furnace reactors
Dispenser is linked in sequence, and 1# rotary furnace entrance has the screw feeder of connection feed bin；1#-4# rotary furnace inlet is separately connected pair
The evaporator for the reactant vapor/carrier gas mixed gas answered, or it is directly connected to carrier gas source；1#-4# rotary furnace exit difference
Connect device for absorbing tail gas；4# rotary furnace exit is also connected with catalyst prod storehouse.
The present invention, in the device for preparing catalyst, 1#-4# rotary furnace is horizontal inclined placement, and arrival end is high, outlet
Hold it is low, level inclination be 5-10 °；For 4 rotary furnaces there are difference in height, mounting height is 1# rotary furnace > 2# rotary furnace > 3# revolution
Furnace > 4# rotary furnace, allows screw feeder horizontal tilt angle to remain 20-40 °；There is pusher to scrape on 4 rotary furnace inner walls
Plate guarantees that carrier granular can realize continuous discharge.
In the present invention, in the device for preparing catalyst, 1# rotary furnace is activated centre gas-phase deposition reactor, 2# times
Converter is high-temperature process reactor, 3# rotary furnace is water processing reactor, and 4# rotary furnace is silanization treatment reactor.
A kind of purposes of the catalyst, the catalyst are used for epoxidation reaction of olefines, are preferred for C3~C10Straight chain
Alkene, C3~C10Isomeric olefine, C6~C16Cyclenes and C6~C16One or more epoxidation reaction in aromatic olefin.
In the present invention, the oxidant in epoxidation reaction is organic peroxide, preferably tert-butyl hydroperoxide, ethylbenzene
It is one or more in hydrogen peroxide and cumyl hydroperoxide.
In the present invention, the epoxidation reaction is the liquid phase epoxidation reaction of alkene and oxidant.
In the present invention, the catalyst of preparation is used to be catalyzed the process conditions of preparing epoxypropane by epoxidation of propene are as follows: reaction
40~120 DEG C of temperature, pressure is 2~4.5MPa, and the molar ratio of propylene and oxidant is (3~10): 1, mass space velocity is 1~
5h-1；Purified propylene>99.5%, system moisture content<100ppm.
In the present invention, when amplifying the catalyst of preparation for preparing epoxypropane by epoxidation of propene reaction system, oxidant
Conversion ratio > 99.1% (because of alkene excess, generally characterizes conversion ratio with oxidant), to the average selectivity > of propylene oxide
92.7%.
Method for preparing catalyst of the present invention solves hydro-thermal method prepare catalyst Step cumbersome, titanium source, silicon source hydrolysis
Speed mismatch causes control difficulty big, and causes catalyst preparation is at high cost to ask using organic titanium source and macromolecular template agent
Topic；It solves in tube furnace reactor that prepare carrier thermal coefficient existing for catalyst using vapour deposition process low simultaneously, rises
Temperature fall time is long, the problem for causing catalyst preparation efficiency relatively low.To realize the continuous extensive life of epoxidation catalyst
It produces.
The present invention has the positive effect that:
(1) easy to operate in catalyst preparation process, solve a reaction in existing catalyst batch process preparation process
The problems such as frequent heating and cooling of device and frequent replacement raw material, the preparation efficiency of catalyst is substantially increased, realizes the company of catalyst
Continuous large scale preparation, the production efficiency of catalyst can achieve 100~400kg/h；
(2) catalyst-assembly design rationally, makes solid particulate reagent realize continuous flowing between each reactor, can
To be successively continuously finished multiple steps of catalyst preparation under the conditions of differential responses；
(3) catalyst for using the continuous large scale preparation of the method for the invention, prepares epoxy third for epoxidation of propylene
When alkane, oxidant conversion ratio > 99.1%, to the average selectivity > 92.7% of propylene oxide.
Detailed description of the invention
Fig. 1 is the schematic diagram of catalyst preparation device in the present invention.
Specific embodiment
In order to be best understood from the present invention, below with reference to embodiment the present invention is furture elucidated content, but the contents of the present invention
It is not limited solely to the following examples.
The rotary furnace that catalyst preparation process uses is the production of Xianyang blue light thermal technology Science and Technology Ltd..
Carrier is the silica gel particle after being dried, and size distribution is 0.2~2mm, and aperture is 5~15nm, specific surface
Product is 200~500m2/ g, water content≤2wt%, the production of Qingdao bay Fine Chemical Co., Ltd.
Primary raw material information is as shown in the table:
| Raw material | Producer and purity |
| TiCl4 | Aladdin is analyzed pure (>=99%) |
| TiF4 | Western Gansu Province chemical industry is analyzed pure (>=99%) |
| Hexamethyldisilazane | Aladdin is analyzed pure (>=98%) |
| EBHP | Self-control, 32%-35% (ethylbenzene and ethylbenzene hydroperoxide mixed solution) |
| CHP | Aladdin, >=80% |
| Propylene | Yantai profit dragon, it is high-purity (>=99.995%) |
| N2 | Hewlett-Packard in Beijing, it is high-purity (>=99.995%) |
The measurement of peroxide conversion ratio in epoxidation reaction is carried out using following methods:
In the epoxidation reaction carried out using catalyst prepared by each embodiment and comparative example, the conversion ratio of peroxide is surveyed
Iodimetric titration is used, potentiometric titrimeter used in titration step therein is produced by Wan Tong company, Switzerland, model 916Ti-
Touch。
1, iodometric determination EBHP/CHP conversion ratio specific steps:
(1) 20mL glacial acetic acid is added in conical flask, in N2After emptying, 5g or so KI is added；
(2) it takes the analysis sample of 1g or so that the above mixture is added, while preparing blank sample and comparing；
(3) after water seal, magnetic agitation, reacts 30min in the dark；
(4) add pure water 50mL, use the Na for preparing concentration2S2O3Solution is titrated；
(5) according to Na2S2O3The usage amount of solution calculates the total mole number of organic peroxide, and then calculates its conversion ratio.
As following formula calculates:
Wherein, VNa2S2O3For the Na of consumption2S2O3The volume of solution, CNa2S2O3For the Na used2S2O3Solution it is mole dense
Degree；
2, the measurement of the epoxidation product selectivity in epoxidation reaction
It is carried out in epoxidation reaction using catalyst prepared by each embodiment and comparative example, the selectivity of epoxidation product is surveyed
Pinged gas-chromatography progress.
Gas-chromatography uses the GC-2010Plus of Shimadzu, and analysis condition is as shown in the table:
Gas-chromatography operating condition
The measurement of epoxidation product content is carried out by internal standard method, epoxidation product concentration mensuration is with DMF (dimethyl formyl
Amine) it is solvent, with DT (dioxane) for internal standard compound.Use DMF as solvent the pure epoxidation product as object to be measured,
It is configured to the standard solution of different quality concentration, takes each standard solution and internal standard compound of fixed mass respectively, sample introduction point after mixing
Analysis.To each standard solution, with the ratio between the peak area of epoxidation product and DT in chromatogram for x, epoxidation product is in each standard
Mass concentration (%) in solution is y, obtains internal standard standard curve y=(ax-b) × 100%, guarantees R2Coefficient >=0.999.So
Afterwards, the mixture in system after reaction is sampled, sample is diluted using internal standard substance solution, and is divided with gas-chromatography
Analysis, wherein after dilution in solution to be measured the quality of internal standard compound with drafting standard curve when use it is identical in quality, it is to be measured after dilution
The gross mass of solution is identical as sample introduction gross mass when drawing standard curve.As following formula calculates:
The mass concentration of epoxidation product=(a × (AEpoxidation product/ADT)-b) × extension rate × 100%
Wherein, A is subscript substance corresponding peak area in chromatogram；Extension rate is the liquor capacity to be measured after dilution
Multiple relative to the sample volume before dilution.
Epoxidation product content=epoxidation product mass concentration × sample quality in sample
The peroxide (EBHP, CHP etc.) for epoxidation product selectivity=epoxidation product gross mass/actually convert
Theoretically can oxyalkylene generate epoxide quality × 100%
Embodiment 1
The preparation that catalyst is carried out using attached continuous rotary kiln reactor shown in FIG. 1, by the inclination angle of 1#-4# rotary furnace
Degree is disposed as 8 °, and mounting height is 1# > 2# > 3# > 4#, makes 20 ° of screw feeder tilt angle, is then turned on connection
The screw feeder of converter, according to SiO2Charging rate sets dispenser revolving speed；After dispenser stabilization of speed, enter from converter
Mouth is passed through nitrogen at room, measures offgas outlet nitrogen flow, determines converter and passes in and out the air-tightness of gas pipeline.
After the completion of preparation, converter heating is opened, 1#~4# rotary furnace is warming up to 150 DEG C, 500 DEG C, 250 DEG C respectively
With 150 DEG C；Converter revolving speed is set as 5r/min；By preheater by reactant vapor and/or N2It is preheated, 1#~4# furnace is logical
The reactant vapor and/or N entered2It is preheated to 150 DEG C, 500 DEG C, 250 DEG C and 150 DEG C respectively, in the gas that wherein 1# furnace is passed through
The TiCl for being 5%v/v containing concentration4Steam, gas flow 10Nm3/h；The gas that 2# furnace is passed through is purity >=99.5%
N2, gas flow 20Nm3/h；The gas that 3# furnace is passed through contains the water vapour that concentration is 5%v/v, and flow is 15N m3/h；4#
The gas that furnace is passed through contains the hexamethyldisilazane steam that concentration is 10%v/v, and flow is 5N m3/h；
After test converter exit gas composition is consistent with entrance, it is continuously added to using screw-feeder into 1# converter entrance
Silica-gel carrier particle, charging rate 100kg/h, silica gel successively pass through 1#~4# rotary furnace, the reaction in every rotary furnace
Residence time is 4h.Silica-gel carrier carries out at activated centre vapor deposition, high-temperature process, water process and silanization respectively in furnace
Four reaction steps are managed, catalyst is entered in catalyst feed bin by 4# converter outlet to cool down, and is cooled to room temperature and carries out screening collection
Epoxidation catalyst finished product is obtained, catalyst number is A.
Embodiment 2
The preparation that catalyst is carried out using attached continuous rotary kiln reactor shown in FIG. 1, by the inclination angle of 1#-4# rotary furnace
Degree is disposed as 5 °, and mounting height is 1# > 2# > 3# > 4#, makes 30 ° of screw feeder tilt angle, is then turned on connection
The screw feeder of converter, according to SiO2Charging rate sets dispenser revolving speed；After dispenser stabilization of speed, enter from converter
Mouth is passed through nitrogen at room, measures offgas outlet nitrogen flow, determines converter and passes in and out the air-tightness of gas pipeline.
After the completion of preparation, converter heating is opened, 1#~4# rotary furnace is warming up to 200 DEG C, 650 DEG C, 300 DEG C respectively
With 250 DEG C；Converter revolving speed is set as 9r/min；By preheater by reactant vapor and/or N2It is preheated, 1#~4# furnace is logical
The reactant vapor and/or N entered2It is preheated to 200 DEG C, 650 DEG C, 300 DEG C and 250 DEG C respectively, in the gas that wherein 1# furnace is passed through
The TiCl for being 10%v/v containing concentration4Steam, gas flow 15Nm3/h；The gas that 2# furnace is passed through is purity >=99.5%
N2, gas flow 20Nm3/h；The gas that 3# furnace is passed through contains the water vapour that concentration is 7.5%v/v, and flow is 20N m3/h；
The gas that 4# furnace is passed through contains the hexamethyldisilazane steam that concentration is 15%v/v, and flow is 10N m3/h；
After test converter exit gas composition is consistent with entrance, it is continuously added to using screw-feeder into 1# converter entrance
Silica-gel carrier particle, charging rate 300kg/h, silica gel successively pass through 1#~4# rotary furnace, the reaction in every rotary furnace
Residence time is 3h.Silica-gel carrier carries out at activated centre vapor deposition, high-temperature process, water process and silanization respectively in furnace
Four reaction steps are managed, catalyst is entered in catalyst feed bin by 4# converter outlet to cool down, and is cooled to room temperature screening collection and obtains
Epoxidation catalyst finished product, catalyst number is B.
Embodiment 3
Using attached continuous rotary kiln reactor shown in FIG. 1, (1# rotary furnace reaction gas is TiF4) carry out catalyst system
It is standby, the tilt angle of 1#-4# rotary furnace is disposed as 10 °, mounting height is 1# > 2# > 3# > 4#, and screw feeder is made to incline
Rake angle is 40 °, the screw feeder of connection converter is then turned on, according to SiO2Charging rate sets dispenser revolving speed；Wait give
After glassware stabilization of speed, it is passed through nitrogen at room from converter entrance, measures offgas outlet nitrogen flow, determines converter and disengaging tracheae
The air-tightness of line.
After the completion of preparation, converter heating is opened, 1#~4# rotary furnace is warming up to 300 DEG C, 800 DEG C, 400 DEG C respectively
With 300 DEG C；Converter revolving speed is set as 3r/min；By preheater by reactant vapor and/or N2It is preheated, 1#~4# furnace is logical
The reactant vapor and/or N entered2It is preheated to 300 DEG C, 800 DEG C, 400 DEG C and 300 DEG C respectively, in the gas that wherein 1# furnace is passed through
The TiF for being 15%v/v containing concentration4Steam, gas flow 15Nm3/h；The gas that 2# furnace is passed through is purity >=99.5%
N2, gas flow 20Nm3/h；The gas that 3# furnace is passed through contains the water vapour that concentration is 10%v/v, and flow is 20N m3/h；4#
The gas that furnace is passed through contains the hexamethyldisilazane steam that concentration is 25%v/v, and flow is 10N m3/h；
After test converter exit gas composition is consistent with entrance, it is continuously added to using screw-feeder into 1# converter entrance
Silica-gel carrier particle, charging rate 400kg/h, silica gel successively pass through 1#~4# rotary furnace, the reaction in every rotary furnace
Residence time is 6h.Silica-gel carrier carries out at activated centre vapor deposition, high-temperature process, water process and silanization respectively in furnace
Four reaction steps are managed, catalyst is entered in catalyst feed bin by 4# converter outlet to cool down, and is cooled to room temperature and carries out screening collection
Epoxidation catalyst finished product is obtained, catalyst number is C.
Comparative example 1
Ti-MCM-41 epoxidation catalyst is prepared using hydrothermal synthesis method.
Tetraethyl ammonium hydroxide (TEAOH) aqueous solution for configuring 25wt% concentration, 35.0g ethyl orthosilicate (TEOS) is existed
In the 29.7g tetraethyl ammonium hydroxide aqueous solution being added dropwise to dropwise under stirring condition, mixed liquor A is formed；By four fourth of 1.2g metatitanic acid
Ester (TBOT) is added dropwise to dropwise in the 25.1g triethanolamine (TEA) under stirring, forms mixed liquid B；Mixed liquid B is dripped dropwise again
Enter in the mixed liquor A under stirring, after stirring 1h, then 11.0g deionized water (H is added dropwise2O) stir 0.5h, the amount of forming material it
Than for 1.0TEOS:0.02TBOT:0.3TEAOH:1TEA:11H2The homogeneous phase solution of O.It is protected from light place aging 48h in room temperature；Drum
100 DEG C of forced air dryings for 24 hours, obtain dry white chunks particle in wind drying box；180 DEG C of rotations in homogeneous reactor after milling
Turn heat treatment 4h；Template agent removing finally is removed with the heating rate of 5 DEG C/min, 600 DEG C of roasting 10h in Muffle furnace, Ti- is made
MCM-41.The molecular sieve after roasting is subjected to silanization treatment, silanization treatment temperature and silylating reagent dosage again and is implemented
4# converter in example 1 is identical, Ti-MCM-41 epoxidation catalyst original powder is made after the completion of silanization treatment, then add silica solution
Extruded moulding is carried out, catalyst after molding is denoted as DB-1.DB-1 catalyst preparation process is prepared by interval, total needed for each step
Time is 100h or so, and since hydrolysis reaction need to be controlled accurately, the more difficult amplification of single batch catalyst preparation amount.
Comparative example 2
Using conventional four step interval legal system epoxidation catalyst of single-reactor.
By 50kg SiO2Carrier is added in the tubular reactor that internal diameter is 400mm, and furnace temp is set as 350 DEG C,
Constant temperature 20h reaches 350 DEG C after balancing silica gel bed temperature, and 5h is handled at 350 DEG C, is cooled down after the completion of processing；It has handled
Reaction tube temperature is successively risen to 200 DEG C, 650 DEG C, 300 DEG C and 180 DEG C after, respectively carry out the activated centre Ti deposition process,
Roasting process, water treatment procedure and silanization treatment.Wherein Ti center deposition process is using N2With TiCl4Steam mixing is laggard
Enter reactor to be reacted, TiCl4Dosage 17kg；Steam treatment process is to enter to react after mixing nitrogen with water vapour
Device, the total dosage 20kg of water；Silanization treatment process is to enter reactor, silicon after mixing nitrogen with hexamethyldisilazane steam
Alkylators dosage is 30kg.It completes the time required to the complete preparation process of 50kg catalyst to be 120h.After the reaction was completed by tubular type
Reactor is down to room temperature, and disassembly obtains epoxidation catalyst, is denoted as DB-2.
Embodiment 4
The fixed bed reactors for the use of internal diameter being 30mm load the catalyst of Examples 1 to 3 and comparative example 1,2 respectively, urge
Agent loadings are 20g；With propylene (C3H6) it is raw material, epoxidation reaction, propylene and EBHP raw material are carried out by oxidant of EBHP
Molar ratio be 6:1, feedstock quality air speed be 3h-1, reaction pressure 4.0MPa, reaction temperature is 60 DEG C.Reaction result is shown in Table
1。
As shown in Table 1, in the catalyst of each embodiment and comparative example preparation, epoxy that the present invention is continuously prepared on a large scale
Change catalyst A, B and C propylene oxide selectivity with higher；Meanwhile in terms of EBHP conversion ratio, the embodiment of the present invention is obtained
To catalyst obviously higher than comparative example.The catalyst that the present invention is prepared can be used for the propylene epoxy using EBHP as oxidant
Change reaction, catalyst has preferably reactivity worth.
The reaction result of 1 embodiment 4 of table
Embodiment 5
The fixed bed reactors for the use of internal diameter being 30mm load the catalyst of Examples 1 to 3 and comparative example 1~2 respectively,
Loaded catalyst is 20g；C3H6It is 8:1 with CHP molar ratio, feedstock quality air speed is 5h-1, reaction pressure 4MPa, reaction
Temperature is 80 DEG C.Reaction result is shown in Table 2.
As shown in Table 2: epoxidation catalyst A, B and C ring with higher that method of the invention is continuously prepared on a large scale
Ethylene Oxide selectivity；Meanwhile in terms of CHP conversion ratio, the embodiment of the present invention obtains catalyst obviously higher than comparative example.This
The catalyst that invention is prepared can be used for the propylene ring oxidation reaction using CHP as oxidant, and catalyst, which has, preferably to react
Performance.
The reaction result of 2 embodiment 5 of table
From the above as it can be seen that method for preparing catalyst of the present invention passes through the temperature of control converter reactor, inside
The residence time of gas composition and carrier, the serialization of catalyst difference preparation step may be implemented, and make to be prepared
Catalyst has good activity and selectivity for epoxidation reaction of olefines.
Claims (13)
1. a kind of method of continuous large scale preparation olefin epoxidation catalysts, which is characterized in that this method uses four sequences
The rotary furnace reactor successive reaction of connection prepares catalyst, and preparation step is as follows:
(1) four rotary furnaces of 1#, 2#, 3# and 4# are followed successively by by sequence by raw material, rise to respective reaction temperature respectively, and
It is continuously passed through respective reactant vapor and/or carrier gas respectively, stablizes each in-furnace temperature and gas composition；
(2) carrier granular is continuously added to 1# rotary furnace, and continuously passes sequentially through 1#, 2#, 3# and 4# rotary furnace, divided in each furnace
It carry out not four activated centre vapor deposition, high-temperature process, water process and silanization treatment reaction steps；
(3) 4# rotary furnace outlet material is collected in cooling, and olefin epoxidation catalysts finished product is prepared.
2. method for preparing catalyst according to claim 1, which is characterized in that
In step (1), the reaction temperature of the 1# rotary furnace is 150~300 DEG C, and the gas being passed through is titanium compound steam and N2
Carrier gas；The concentration of titanium compound steam is 5~15%v/v；Titanium compound is selected from titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium
One of sour tetra-ethyl ester, metatitanic acid orthocarbonate and butyl titanate are a variety of；
In step (1), the reaction temperature of the 2# rotary furnace is 500~800 DEG C, and the gas being passed through is the N of purity >=99.5%2；
In step (1), the reaction temperature of the 3# rotary furnace is 250~400 DEG C, and the gas being passed through is water vapour and N2Carrier gas,
Middle water vapour is that deionized water is obtained through evaporation gasification, not metal ion；Water vapor concentration is 5~10%v/ in mixed gas
v；
In step (1), the reaction temperature of the 4# rotary furnace is 150~300 DEG C, and the gas being passed through is organosilan steam and N2
Carrier gas, wherein organosilan is selected from hexamethyldisilazane, hexamethyl chlorine silazane, seven methyl chloride silazane, trimethylchloro-silicane
Alkane, dimethylchlorosilane, tetramethyl-disilazane, dimethyl diethoxysilane, trimethylmethoxysilane, dimethylformamide dimethyl
One of oxysilane and trimethylethoxysilane are a variety of, preferably hexamethyldisilazane；Organosilicon in mixed gas
The concentration of alkane steam is 10~25%v/v.
3. method for preparing catalyst according to claim 1, which is characterized in that will be preheated in step (1) and each revolution
The consistent mixed gas of furnace reaction temperature each leads into each rotary furnace, and gas flow is 5~20Nm3/h；Rotary furnace revolving speed be 3~
10r/min。
4. method for preparing catalyst according to claim 1, which is characterized in that carrier described in step (2) is at dry
SiO after reason2Material, preferably silica gel particle；Its size distribution is 0.2~2mm, and aperture is 5~15nm, specific surface area 200
~500m2/ g, water content≤2wt%.
5. method for preparing catalyst according to claim 1, which is characterized in that step (2) carrier is from 1# rotary furnace entrance
It is added, charging rate is constant, and speed is 100~400kg/h；Reaction time of the carrier in each rotary furnace is 2~6h.
6. method for preparing catalyst according to claim 1, which is characterized in that step (2) during the reaction, needs continuous
The respective preheating reactant vapor of 1#-4# rotary furnace and/or carrier gas are supplemented, each in-furnace temperature and gas composition are stablized.
7. method for preparing catalyst according to claim 1, which is characterized in that step (3) 4# rotary furnace outlet material drop
It is screened to obtain finished catalyst after warming to room temperature.
8. a kind of device for preparing catalyst described in any one of claim 1-7, which is characterized in that described device includes four
The rotary furnace reactor of sequential connection is followed successively by 1# rotary furnace, 2# rotary furnace, 3# rotary furnace and 4# by sequence by raw material and turns round
Furnace；It is linked in sequence between four rotary furnace reactors by screw feeder, 1# rotary furnace entrance has the screw feeder of connection feed bin
Device；1#-4# rotary furnace inlet is separately connected the evaporator of the mixed gas of corresponding reactant vapor/carrier gas, or directly connects
Carry gas source；1#-4# rotary furnace exit is separately connected device for absorbing tail gas；4# rotary furnace exit is also connected with catalyst prod
Storehouse.
9. catalyst preparation device according to claim 8, which is characterized in that 1#-4# rotary furnace is horizontal inclined placement,
Arrival end is high, outlet end is low, and level inclination is 5-10 °；For 4 rotary furnaces there are difference in height, mounting height is 1# rotary furnace > 2#
Rotary furnace > 3# rotary furnace > 4# rotary furnace, allows screw feeder horizontal tilt angle to remain 20-40 °；4 rotary furnaces
There is pusher scraper plate on inner wall.
10. catalyst preparation device according to claim 8 or claim 9, which is characterized in that 1# rotary furnace is activated centre gas phase
Deposition reactor, 2# rotary furnace are high-temperature process reactor, 3# rotary furnace is water processing reactor, and 4# rotary furnace is at silanization
Manage reactor.
11. catalyst preparation described in any one of catalyst or claim 8-10 described in a kind of any one of claim 1-7
The purposes of the catalyst of device preparation, the catalyst are used for epoxidation reaction of olefines, are preferred for C3~C10Linear alkene, C3
~C10Isomeric olefine, C6~C16Cyclenes and C6~C16One or more epoxidation reaction in aromatic olefin.
12. the purposes of catalyst according to claim 11, which is characterized in that the oxidant in epoxidation reaction is organic mistake
It is one or more in oxide, preferably tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumyl hydroperoxide.
13. the purposes of 1 or 12 catalyst according to claim 1, which is characterized in that the epoxidation reaction is alkene and oxygen
The liquid phase epoxidation reaction of agent.
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